10 - Chapter 2 PDF

CHAPTER 2
Efficient adsorption of Cr (VI) from

aqueous solution on low cost adsorbent
developed from Limonia acidissima
(Wood apple) shell
* This work has been published in Adsorption Science and
Technology, 28 (6) 2010, 547-560.
Limonia acidissima (Wood apple)
Wood Apple
Wood Apple Shell
Chapter 2
45
2.1 INTRODUCTION
The presence of heavy metals in drinking water sources and in edible
agricultural crops can be harmful to human. It is well known that heavy metals
can be toxic e.g. they damage nerves, liver and bones also they block functional
groups of vital enzymes [1]. Heavy metals are found in water, air and soil. The
major sources of heavy metals in water and soil are waste water streams from
many industrial processes [2]. Heavy metals like chromium, copper, lead, zinc,
mercury, cadmium etc. are present in waste water from several industries such
as metal cleaning and plating baths, refineries, paper and pulp, tanning, dyes
and pigments, wood preserving, glass, ceramic paints, catalysis chemical
manufacturing etc. in which chromium (VI) is present from 5 to 220 mg/dm3
which leave into environment [3-5]. The effluent from industries containing
Cr(VI) is considered by the International Agency for Research on Cancer
(IARC) (1982) as powerful carcinogenic agent that modifies the DNA
transcription process causing important chromosomic aberration [6, 7].
Various technologies are employed for removing toxic ions from water,
which
include
chemical
precipitation, reverse
osmosis,
ion-flotation,
evaporation, ion-exchange and adsorption [8, 9]. Most of these methods suffer
from drawbacks such as incomplete metal removal, high capital and
operational costs, requirements of expensive equipment and monitoring system,
high reagent and energy requirements, generation of toxic sludge, other waste
products that require disposal, membrane scaling, fouling and blocking [10,
11]. Adsorption by activated carbon is one of the effective techniques for
chromium removal from waste water because of high surface area, highly
porous character and relatively low-cost. The use of activated carbon for
removing chromium from waste water has been received a great attention from
decades [12, 13].
Activated carbon was especially known for the effectiveness in
removing organic chemicals from waste water and also for removal of
inorganic and heavy metal pollutants in laboratory as well as in industries [14,
15]. Some authors reported the adsorption of metallic complexes on activated
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
Chapter 2
46
carbon after complexation with chelating agents; e. g. thiourea and bromide ion
for bismuth [16]. Adsorption is an effective and versatile method for removing
chromium. Natural materials that are available in large quantities or certain
waste products from industrial or agricultural operations may have potential as
inexpensive adsorbents.
In present study, Limonia acidissima (wood apple) fruit which is
medicinally important as well as used for making sweet and shell of these fruits
are waste. After the use of fruit, the shell is unwaged. Shell of this fruit is tough
and it was proposed to prepare activated carbon which rendered good
adsorption capacity.
2.2 LITERATURE SURVEY OF REMOVAL OF CHROMIUM (VI)
The removal of toxic metal ions from waste water is an important and
widely studied research area. One of the heavy metal that has been a major
focus in waste water treatment is chromium. The toxicity caused by hexavalent
chromium is high and therefore priority is given to regulate this pollutant at the
discharge level. The adsorption process has been widely used all over world
for the same. The various adsorbents have been used for removal of Cr(VI) like
silica gel, polymer, carbon nanotubes, fly ash, clays, zeolites, chitosan, peat
moss, biosorbent, food waste etc.
In recent years, the researchers have developed many adsorbents,
sometimes the adsorbents are used as it is or impregnated or modified to
improve the capacity of the adsorption. The river sand has been used for
adsorption of Cr(VI) which had 0.15 mg/g adsorption capacity with 74.3%
removal capacity [17]. S.M. Lee et al. (2010) have prepared Manganese-coated
sand by wet coating method and reported improvement in adsorption capacity
up to 6.27 mg/g [18]. Silica gel, alumina, montmorillonite, kaolin, tobermorite
and magnetite were explored as adsorbents for adsorption of Cr(VI). The
removal capacity for Cr(VI) was observed to be more than 80% [19]. The silica
gel modified with a reactive polymer, alkyl quaternized poly(4-vinylpyridine)
is reported. NaOH was used to desorb Cr(VI) up to 90% and coated silica gel
ADSORBENTS
Chapter 2
47
could be reused [20]. The polyaniline nanomaterials were also used to graft the
silica gel, which had particle size, adsorption capacity, and surface area of the
material to be 100 nm, 135 mg/g and 720 m2/g respectively [21]. A crosslinked graft copolymer of [2-(methacryloyloxy)ethyl] trimethylammonium
chloride on poly(vinyl alcohol) has been synthesized and it is crosslinked by
glutaraldehyde for the adsorption of Cr(VI), which shows adsorption
efficiency of 6.69 mg/g from aqueous solution at 300 K [22]. I.S. Ahamed et al.
(2008) were reported the synthesis of some polymers, first polyvinyl chloride
(PVC) was aminated by the resin with concentrated aqueous solution of
ethylene diamine. The aminated PVC was then reacted with 4, 4- methylene
diphenyldiisocyanate (DMI) to incorporate the isocyanate group on polymer
backbone. The isocyanate PVC was further reacted with castor oil. Second
polymer poly (ester-urethane-acrylate) (PEUA) was polymerized in two step
process. Third type of polymer was carboxymethyl poly (urethane-acrylate)
which was modified with carboxylic group. These resins were used to remove
the heavy metals, amongst them Cr(VI) ion was adsorbed to 98.2% at 293 K
[23]. The literature survey shows several polymers with there good adsorption
capacity such as, polyaniline/poly ethylene glycol with 109.9 and 68.97 mg/g
respectively [24]. The Chromium (VI) percentage removal capacity was
reported for quaternized crosslinked poly (4-vinylpyridines) [25] and aminated
polyacrylonitrile fibers [26] as 97.4% and 96% respectively. The adsorbents
reported with their adsorption capacity such as, condensed-tannin gels derived
from a natural polymer with polyhydroxyphenyl group (287 mg/g) [27], short
chain polyaniline (PANI), a polymer was synthesized on the surface of jute
fiber (62.9 mg/g) [28], ethylenediamine-modified cross-linked magnetic
chitosan resin (51.813 mg/g at 293 K) [29]. These reported methods are having
multi step synthesis, as well as the dose of adsorbent is too high and thus these
methods are not economical.
The modification over to the naturally occurring adsorbent is nowadays
inevitable. The naturally occurring zeolite was used by the modification with
various agents. The natural zeolite like Pohang zeolite and Haruna zeolite
ADSORBENTS
Chapter 2
48
modified with surfactant hexadecylpyridinium bromide was investigated which

had shown the better change in capacity [30]. Natural zeolite, mordenite was
modified with the cationic surfactants like, ethylhexadecyldimethylammonium
(EHDDMA), and hexadecyltrimethyl-ammonium (HDTMA-HSO4) which
shows the adsorption capacity as HDTMA-HSO4>EHDDMA>mordenite.
Treated zeolite showed the greatest chromate sorption (93%) [31]. Natural
zeolite was modified with hexadecyltrimethylammonium (HDTMA) bromide
surfactant which found to be 3.1 mg/g adsorption capacity while natural zeolite
without modification had 0.14 mg/g adsorption capacity [32]. Some researchers
have used various agents to improve the capacity of natural zeolite such as,
bolaform N, N, N, N, N, N - hexamethyl - 1,9-nonanediammonium dibromide
reagent [33], clinoptilolite samples modified with HNO3 or NaOH [34].
Sodium chloride modified zeolites shows the adsorption capacity 3.23 mg/g as
compared with natural zeolite, 1.79 mg/g [35]. Synthetic Zeaolite 4A shows
96% and 55.3% adsorption capacity respectively at pH 11 and 3 [36]. The
Zeolite NaX adsorbs 6.414 mg/g Cr(VI) from aqueous solution [37].
Clays are well known adsorbent used for heavy metal removal. Acid or
other reagents are used for activation of clays. The clays are extremely fine
particles exhibiting chemical properties of colloids. Kaolinite and its modified
forms,
acid-activated
kaolinite,
poly(oxozirconium)
kaolinite,
and
tetrabutylammonium kaolinite were investigated by K.G. Bhattacharyya et al.

(2006) for adsorption of Cr(VI). The Langmuir monolayer capacity of the clay
adsorbents is from 10.6 to 13.9 mg/g [38]. Acid activation of Resadiye clays,
Hancili clays was done with H2SO4 and HCl; adsorption capacity were found to
be 1.40, 0.75 and 0.884 mg/g for H, H-HCl, and H-H2SO4 and 1.85, 1.44 and
2.20 mg/g for R, R-HCl and R-H2SO4, respectively [39]. Bentonite clay has
been modified by several treatments such as aluminium pillaring, acid
activation and pillared followed by acid activation which shows 50 to 113 mg/g
adsorption capacity [40].
Carbon nanotubes (CNTs) have attracted great attention since their
discovery because of their small size, large surface area, unique hollow
ADSORBENTS
Chapter 2
49
structure, high mechanical strength and remarkable electrical conductivity.

According to the carbon atom layers on the sidewalls of the nanotubes, CNTs
can be visualized as a sheet of graphite that has been rolled into a tube and
divided into single walled carbon nanotubes (SWCNTs) and multiwalled
carbon nanotubes (MWCNTs). The oxidized MWCNT may be promising
materials in environmental pollution management [41]. MWCNT developed by
chemical vapor deposition of acetylene in hydrogen flow at 1033 K using NiFe nanoparticles as catalysts (Fe(NO3)2 and Ni(NO3)2 were treated by sol-gel
process and calcinations to get FeO and NiO, and then deoxidized by H2 to get
Fe and Ni as catalysts. The developed MWCNTs were used to remove Cr(VI),
which shows the maximum adsorption capacity to be 4.434 and 4.2615 mg/g in
two cases [41, 42]. K. Pillay et al. (2009) found unfunctionalised multi-walled
carbon nanotubes which showed the highest adsorption capability up to 98% of
a 100 ppb Cr(VI) solution being adsorbed [43]. In another case imidazole
functionalized sol-gel adsorbent had 152 mg/g adsorption capacity [44], while
montmorillonite-supported
magnetite
nanoparticles
prepared
by
co-
precipitation and hydrosol method show the 20.16 and 13.88 mg/g adsorption
capacity respectively while unsupported magnetite had 10.6 mg/g adsorption
capacity [45].
Nowadays, number of adsorbents are developed. Chitosan, the major
derivative of chitin and second abundant biopolymer in nature after cellulose, is
also used as adsorbent which showed 22.09 mg/g adsorption capacity [46].
Natural and crosslinked chitosan membranes were used as adsorbent, for
Cr(VI) with 65.7 and 1420 mg/g adsorption capacity respectively [47].
Sphagnum moss peat was reported as adsorbent for Cr(VI) with 119.0 mg/g
adsorption capacity [48]. The low rank Turkish brown coals (Ilgn: BC1,
Beysehir: BC2 and Ermenek: BC3) were employed as adsorbent to remove
Cr(VI) from aqueous solutions witch shown adsorption capacity of 58.24,
64.48 and 38.48 mg/g respectively [49]. Various industrial wastes has shown
the adsorption capacity for Cr(VI) such as distillery sludge (5.7 mg/g) [50], red
ADSORBENTS
Chapter 2
50
mud, an aluminium industry waste (226.72 mg/g) [51]. Tea factory waste has
been also reported for Cr(VI) adsorption with capacity of 54.65 mg/g [52].
Application of fly ash, a waste material, for the removal of chromium
from aqueous solutions and waste water has been investigated. The fly ash
from Patratu Thermal Power Station had shown 89.12% removal and 0.266
mg/g adsorption capacity of Cr(VI) at 298 K [53]. Turkish fly ashes; AfsinElbistan and Seyitomer have shown 25.46 and 30.91% removal and 0.1489 and
0.0162 mg/g adsorption capacity respectively [54], for sugar industry waste i.e.
bagasse fly ash 98% removal was reported with 4.35 mg/g adsorption capacity
[55]. Coal fly ash was used successfully with 18.28 mg/g capacity of
adsorption but the adsorbent amount is high as well as 6 h time is required for
equilibrium [56]. Fertilizer industries generate large amounts of carbon slurry
waste due to incomplete combustion of oil fuel. This dried slurry as cake
material, available at a very cheap rate was converted into an effective and
efficient adsorbent for the removal of hexavalent chromium from aqueous
solutions with 15.24 mg/g maximum adsorption [13].
The biosorption experiments were carried out to remove Cr(VI) using
Bacillus subtilis, Pseudomonas aeruginosa and Escherichia cloacae in batch
systems which showed 10.526, 3.496 and 25.641 mg/g adsorption capacity but
major problem about this treatment is that, this method is time consuming [57].
P. aeruginosa and B. subtilis are having very less contact time of only 23 min
and 0.5 g adsorbent dosage but it has very less adsorption capacity of only 1.44
mg/g [58]. The ability of a biofilm of E. coli supported on kaolin to remove
Cr(VI), Cd(II), Fe(III) and Ni(II) from aqueous solutions was investigated in
batch assays for the treatment of diluted aqueous solutions. For Cr(VI), the
removal was 100% for the lower concentration (8 mg/dm3) tested and around
20% for the higher concentration (16 mg/dm3) [59]. For Aspergillus sp. and
Hirsutella sp. it was observed that 70% Cr(VI) was removed after 3 days [60].
Biological dead mass is major adsorbent applied to remove the heavy
metals from aqueous solution. In these adsorbents, the material is used as it is
only with minor modification or by improving the capacity by impregnating
ADSORBENTS
Chapter 2
51
reagent. In the biosorption the biomass ingredient are playing a vital role with
respect to adsorption capacity. The lignin and cellulose are major constituents,
which are responsible for adsorption of Cr(VI) as reported by Vinodhini and
Das (2009). The adsorption capacity with raw neem saw dust was observed to
be 58.82 mg/g while without cellulose and without lignin it was 25.64 mg/g
and 10.63 mg/g respectively [61]. The adsorption of chromium (VI) from the
aqueous phase on dried roots of water hyacinth revealed a very high degree of
removal efficiency (almost 100%) [62]. Beech (Fagus orientalis L.) sawdust
had shown 100% as maximum adsorption efficiency at pH 1 [63]. The
maximum Cr(VI) ion sorption capacities of walnut (Juglans regia), hazelnut
(Corylus avellana) and almond (Prunus dulcis) were 8.01, 8.28 and 3.40 mg/g
and percentage removal were 85.32%, 88.46% and 55.00% respectively [64].
D. Park et al. (2007) had shown reliable evidences that the removal
mechanism of Cr(VI) by natural biomaterials is adsorption-coupled reduction.
Sixteen natural biomaterials were used to study not only the Cr(VI)
biosorption, but also total chromium in the aqueous phase. Removal efficiency
of total chromium by each biomaterial was not related with the removal rate of
Cr(VI); pine bark showed the best removal efficiency of total chromium, but
enteromorpha showed the poorest one. The existence of total chromium in the
aqueous phase implies the occurrence of Cr(VI) reduction to Cr(III) when
brought into contact with the biomaterials.
The removal rate of Cr(VI)
depended on the types of biomaterials; the order was pine needle, pine bark >
pine cone, banana skin, green tea waste > oak leaf > Rhizopus, Ecklonia >
Sargassum, walnut shell, rice straw, peanut shell > sawdust, Enteromorpha,
orange peel > rice husk. The pine needle completely removes Cr(VI) in 5 h,
while Ecklonia and rice husk needed 126 h and 1270 h for the complete
removal of Cr(VI) respectively. The removal efficiency in percentage of pine
needle 38.0, pine bark 85.0, pine cone 71.8, banana skin 25.5, green tea waste
64.8, oak leaf 48.7, rhizopus 27.2, ecklonia 77.2, sargassum 64.1, walnut shell
24.6, rice straw 26.3, peanut shell 41.0, sawdust 19.9, enteromorpha 15.8,
orange peel 49.9, rice husk 25.2 is reported [65].
ADSORBENTS
Chapter 2
52
The bisorption by various biosorbents such as coconut shell, wheat bran

and rice bran have been reported. Coconut shell had Langmuir adsorption
capacity 1.23 mg/g and Freundlich capacity was 4.182 mg/g with 80% removal
[66], wheat bran had 87.8% removal in 1 h with 0.942 mg/g adsorption
capacity at pH 2 [67]. The rice bran as an adsorbent is used to remove the metal
ions from aqueous solutions, and the sorption capacity was strongly dependent
on the nature and the initial metal ions concentration, initial pH and rice bran
concentration showed 0.069 mg/g Freundlich adsorption capacity [68].
Adsorption capacities of some other adsorbents of food waste such as cooked
waste tea (30.39 mg/g) [69], coconut shell (1.70 mg/g), coconut husk (2.57
mg/g) [2], potato peel waste (8.012 mg/g) are also reported [70]. Along with
this agro waste such as, sunflower stem was investigated for removal of Cr(VI)
with adsorption technique. Pre-boiled sunflower stem and formaldehyde treated
sunflower stem have 4.9 and 3.6 mg/g adsorption capacity and 81.7 and 76.5%
removal capacity respectively [71].
The following factors affect the biosorption process,
(a) Temperature seems not to influence the biosorption performances in the
range of 293-308 K. (b) pH seems to be the most important parameter in the
biosorptive process; it affects the solution chemistry of the metals, the activity
of the functional groups in the biomass and the competition of metallic ions. (c)
For lower values of biomass concentrations there is an increase in the specific
uptake and increase in biomass concentration which leads to interference
between the binding sites. (d) Biosorption is mainly used to treat wastewater
where more than one type of metal ions would be present; the removal of one
metal ion may be influenced by the presence of other metal ions [72].
To overcome such problems several researchers have treated the
biomass, such as neem leaves which had 14.38 mg/g adsorption capacity [73]
and same material after acid treatment gets activated and found to shown
enhanced adsorption capacity to 62.97 mg/g for Cr(VI) [74]. Kratochvil et al.
were studied Sargassum sea weed biomass with 1022 mg/g initial
concentration, it adsorbs 60.0 mg/g of Cr(VI) [75], while A. Saravan et al.
ADSORBENTS
Chapter 2
53
(2009) were studied zinc and chromium biosorption process by Sargassum and
the maximum uptake of chromium and zinc was 65% (21.60 mg/g) and 53%
(21.32 mg/g) respectively [3]. The rice husk and saw dust treated with H2SO4 has shown the 91.75% and 94.33% removal of Cr(VI) respectively [76]. The
active constituent lignocellulosic substrate derived from the industrial treatment
of wheat bran had 35 mg/g adsorption capacity of Cr(VI) [77]. Same way
agricultural waste, sugarcane bagasse was treated with succinic acid for better
adsorption with adsorbent dose 20 g/dm3, pH 2.0 and stirring speed 250 rpm
and investigated 92% removal of Cr(VI) [78].
Activated carbon adsorption seems to be an attractive choice for
chromium removal both for its removal efficiency and for the rapid adaptation
to pollutant loading alteration. For these reasons, activated carbon adsorption
has been widely used for the treatment of waste water containing chromium.
Adsorption isotherms of chromium ions in aqueous solution on a granular
activated carbon (GAC) and on a Char of South African coal (CSAC) have
been studied. The adsorption capacity for the GAC strongly depends on pH of
solution and salinity, with maximum values around 7 mg/g at neutral pH and
low salinity levels. The CSAC shows a smaller adsorption capacity, near 0.3
mg/g, which slightly decreases by increasing pH and salinity levels [79]. Fresh
activated carbon and waste activated carbon were pretreated by heating with
mineral acids H2SO4 and HNO3 at high temperature to prepare several grades
of adsorbents and their Langmuir isotherm maximum adsorption capacities
were reported to be 7.485 and 10.929 mg/g respectively [5]. A composite
adsorbent was prepared by coating poly(4-vinylpyridine) on a granular
activated carbon, followed by cross-linking and quaternization processes which
estimated maximum equilibrium uptake of Cr(VI) 53.7 mg/g at pH 2.25 [80].
However, commercially available activated carbons may be expensive
and, for this reason, the knowledge of the optimal working conditions to
maximize the adsorbent capture capacity is required. Similarly, the production
of low cost, disposable adsorbents for chromium removal is also worth
considering. In recent years, development of surface modified activated
ADSORBENTS
Chapter 2
54
carbons using plant biomass is generating a diversity of activated carbon with

superior adsorption capacity. These are available in large quantities and can be
disposed of without regeneration due to their lower cost. A variety of natural
plant biomass like bael fruit (Aegle marmelos correa) shell had shown 17.27
mg/g adsorption capacity [81]. Groundnut husk was used because of their
inherent high densities and carbon contents after treating with concentrated
H2SO4 in 4:3 ratio and impregnating with silver nitrate to remove Cr(VI) and
found to show 7.01 and 11.4 mg/g adsorption capacity [82]. Rice husk and saw
dust have been used as adsorbent after sulphuric acid treatment to develop
activated carbon with 91.75% and 94.33% removal respectively [83]. The palm
shell activated carbon was prepared by physical activation process with steam
as the activating agent and low molecular weight polyethyleneimine
(LMWPEI) was used as impregnation compound. Palm shell activated carbon
showed adsorption capacity of 12.6 mg/g while modified PEI/palm shell
activated carbon enhanced the adsorption capacity to 20.5 mg/g [84]. A novel
approach to prepare activated carbon from blue-green algal bloom residue has
been tried which was successful with maximum adsorption capacity of 155.52
mg/g in an acidic medium, which is comparable to best result from activated
carbons derived from biomass [85].
Adsorption capacity of Cr(VI) on Hevea Brasilinesis (Rubber wood)
sawdust activated carbon was investigated in a batch system, in which chemical
activation of the saw dust was done with impregnating agent phosphoric acid.
Activation of the pretreated saw dust was carried out in a muffle furnace, the
temperature and time of carbonization being 673 K and 1 h, which show
adsorption capacity of 44.05 mg/g [86], while oak saw dust was impregnated
by HCl was found to show 93.4% removal and 1.72 mg/g adsorption capacity
[87]. Some low cost activated carbons were developed and reported with their
Cr(VI) adsorption capacity such as; coconut tree saw dust (3.46 mg/g) [88],
banana bark (12.57 mg/g) [89], wheat straw (21.34 mg/g) [90]. The percentage
removal of Cr(VI) with rice straw [91] and almond shells [8] were reported as,
95.4% and 98.00% respectively. Activated carbon derived from coconut fibers
ADSORBENTS
Chapter 2
55
(FAC), activated carbon derived from coconut shells (SAC), activated carbon
derived from acid-treated coconut fibers (ATFAC) and activated carbon
derived from acid treated coconut shells (ATSAC) showed 21.75, 9.53, 9.86
and 11.51 mg/g adsorption capacity respectively [92]. Coconut shell charcoal
(CSC) and commercial activated carbon (CAC) for Cr(VI) removal were
investigated in batch studies. Surface modifications of CSC and CAC with
chitosan and oxidizing agents, such as sulfuric acid and nitric acid respectively,
conducted to improve removal performance. CSC and CAC, which have been
oxidized with nitric acid shows higher Cr(VI) adsorption capacities (CSC:
10.88 mg/g, CAC: 15.47 mg/g) than those oxidized with sulfuric acid (CSC:
4.05, CAC: 8.94 mg/g) and non-treated CSC coated with chitosan (CSCCC:
3.65 mg/g), respectively [93].
Activated rice husk carbon was tested along with activated alumina to
remove the Cr(VI) which showed the removal capacity 93.28 and 81.78%
respectively while amount adsorbed by rice husk was 0.8 mg/g [94]. The ability
of waste biogas slurry to remove Cr(VI) from aqueous solution was
investigated which has 5.87 mg/g adsorption capacity [95]. Indian rosewood
sawdust was treated with H2SO4 and formaldehyde. The Cr(VI) removal for
H2SO4 treated carbon was found to be 99.8% while formaldehyde treated
carbon was found to be 87.8%. The amount adsorbed was 10.0 mg/g as higher
capacity [96]. The ficus religiosa leaves were treated with nitric acid and used
for adsorption of Cr(VI) and Pb(II). The adsorption of both had been tested and
found to be 5.66 and 16.95 mg/g respectively [97]. Activated carbon prepared
from sago waste was used to remove Cr(VI) from aqueous solution showed
5.78 mg/g adsorption capacity at 303 K [98]. The Cr(VI) adsorption capacity
of sawdust derived from Shorea robusta (Sal) was found to be 9.55 mg/g and
obeys pseudo second order as kinetic study [99].
In present study, micro porous activated carbon was developed from
Limonia acidissima fruit shell in very simple manner and applied for removal
of Cr(VI) from aqueous solution . It took short time for adsorption and the
adsorption isotherm, kinetics and thermodynamic models were discussed
ADSORBENTS
Chapter 2
56
successively. The activated carbon developed from wood apple shell was
economical and have good quality, so it could be used for further application.
2.3 EXPERIMENTAL
2.3.1 Preparation of materials
Standard stock solution of 1 mg/mL of chromium (VI) was prepared
from potassium dichromate [100]. Sample of Limonia acidissima (wood apple)
was collected from local market. Wood apple was broken and shells were
washed thoroughly with distilled water and kept for sun dry. After drying, the
shells were crushed in small pieces and again washed with deionized water and
dried in oven at 383 K for 24 h. The crushed pieces were soaked in
concentrated H2SO4 (used as impregnating agent) at 1:2 ratio (weight of raw
material / volume of acid) for 24 h. This material was then washed with
deionized water and was kept for activation in muffle furnace at 573 K for 1 h.
The excess acid was washed off with distilled water till neutral pH. The dried
activated carbon powder was then sieved through BSS-25 and used the same
throughout the study.
2.3.2 Characterization of adsorbent
The proximate analysis of activated carbon material was done with
Fourier Transform Infra Red Spectroscopy (FTIR) (Perkin Elmer Spectrum
100), Scanning Electron Microscopy (SEM) (Quanta 3D FEI), and C, H, N, S,
Elemental analyzer (EA 1108, Carlo Erba). The sample on FTIR
characterization shows the functional groups O-H, CH, C=C, S=O, CC
having peak values 3359.52, 2918.72, 1614.94, 1396.66, 1208.28 cm-1
respectively (Fig. 2.1). On the basis of SEM (Fig. 2.2 (a-c)), the micro porous
nature of wood apple shell activated carbon (WASAC) was confirmed. The
elemental analysis and properties of WASAC such as ash content, bulk density
and moisture content are summarized in Table 2.1.
ADSORBENTS
Chapter 2
57
2.3.3 Batch adsorption experiment

Batch adsorption isotherm experiments were conducted by varying
concentrations of Cr(VI) from 90 mg/dm3 to 200 mg/dm3, at constant adsorbent
dose 500 mg/dm3. While adsorbent dosage was varied from 200 mg/dm3 to
500 mg/dm3 at constant concentration of Cr(VI) of 90 mg/dm3. The effects of
time, agitating speed and pH were studied with Cr(VI) concentration of 90
mg/dm3 and an adsorbent dosage of 500 mg/dm3. The concentration of free
Cr(VI) ions in the effluent was determined with 1, 5-diphenyl carbazide (DPC)
in acidic solution spectrophotometrically (Elico SL 171) at max 535 nm [101].
Adsorption isotherm study was done with 90 mg/dm3 Cr(VI) at 299 2
K at pH 2 and time of contact was maintained at 180 min. The agitation was
done at 140 rpm in the Erlenmeyer flasks on an orbital shaker. For the
thermodynamic study, temperature was varied from 303 to 323 K. The
equilibrium adsorption capacity of WASAC was evaluated using the equation,
qe=
(Co-Ce) V
M
(1)
where, qe (mg/g) is the equilibrium adsorption capacity, C0 and Ce are the

initial and equilibrium concentrations (mg/dm3) of Cr(VI) ion solution, V is the
volume and M is the weight of adsorbent.
2.4 RESULT AND DISCUSSION
2.4.1 Effect of pH
The chromium (VI) removal efficiency of WASAC at different pH
values with an initial concentration of 90 mg/dm3 is shown in Fig. 2.3. To each
flask containing 50 mL of Cr(VI) solution, 500 mg of adsorbent was added and
agitated for 3 h at pH varying from 1 to 11 (Table 2.2). After agitation the
whole solution was filtered through Whatmann filter paper no.1 and Cr(VI)
was determined with 1, 5-diphenyl carbazide. The chromium removal
efficiency was 98.05% in the pH range 1-3. For further study pH 2 was used.
ADSORBENTS
Chapter 2
58
Maximum adsorption of Cr(VI) was observed at the acidic pH. This is

because at lower pH there is increase in H+ ions on the carbon surface, and the
presence of HCrO4 ions resulting in significant strong electrostatic attraction.
As the pH increases there was exponential decrease in the Cr(VI) adsorption
and at pH values greater than 6.0 there was no significant adsorption. This was
due to dual competition of both the anions (CrO42 and OH) to be adsorbed on
the surface of the adsorbent of which OH predominates.
H2CrO4 H+ + HCrO4
(2)
HCrO4 H+ + CrO4 2
(3)
2HCrO4 Cr2O7 2 + H2O
(4)
At pH 1.0, the chromium ions exist in the form of H2CrO4, while in the
pH range of 1 6 different forms of chromium ions such as Cr2O7 , HCrO4 ,
Cr3O10
, Cr4O13
coexist of which HCrO4
predominates. As pH increases
this form shifts to CrO4 2 and Cr2O7 2. Chromium exists in different oxidation
states and the stability of these forms depends upon the pH of the system [74,
100].
2.4.2 Effect of time
By keeping all other variables constant, the time was varied from 15
min to 210 min (Table 2.3). Adsorption initiated at 15 min with 39.28% and
reached up to 98.05% from 170 min and the quantity adsorbed was 8.83 mg/g.
There was no significant change in adsorption of Cr(VI) after 170 min (Fig.
2.4). Further study was made at 180 min. The initial rapid rate of adsorption
was may be due to the availability of the positively charged surface of the
adsorbent for anionic Cr(VI) species present in the solution. The later slow
adsorption rate was may be due to the electrostatic hindrance caused by already
adsorbed negatively charged adsorbate species and the slow pore diffusion of
the ions [37]. So up to the 90 min the 80.81% adsorption takes place and after
90 min, the adsorption was increased but the rate of adsorption was slow as
ADSORBENTS
Chapter 2
59
compared with starting rate of adsorption and the equilibrium time was
occurred after 180 min.
2.4.3 Effect of initial concentration of Cr(VI)
The percentage removal of Cr(VI) was 98.05% for 90 mg/dm3 as shown
in Fig. 2.5. As the initial concentration of Cr(VI) was increased from 90
mg/dm3 to 200 mg/dm3, amount adsorbed was increased from 8.83 mg/g to
13.94 mg/g (Table 2.4) at the constant temperature. The pH of the system was
adjusted to 2, and the agitation was done at 140 rpm for 180 min. The amount
adsorbed was increased with increase in concentration of adsorbate. The
percentage removal of Cr(VI) decreases with an increase in initial Cr(VI)
concentration. It may be due to an increase in the number of Cr(VI) ions for the
fixed amount of WASAC. A higher initial concentration provides an important
driving force to overcome all mass transfer resistances of the pollutant between
the aqueous and solid phases, thus increases the uptake. Uptake of the Cr(VI)
also increased with increasing the initial metal concentration tending to
saturation at higher metal concentrations [52].
2.4.4 Effect of adsorbent dosage
The experiments were carried out under the conditions described earlier
and varying adsorbent dosage from 200 mg/dm3 to 500 mg/dm3 (Table 2.5).
The effect of adsorbent dose on the adsorption of chromium by WASAC is
presented in Fig. 2.6. The Cr(VI) removal efficiency increases with increase in
adsorbent dose, since contact surface of adsorbent particles increased and it
would be more probable for HCrO4 and Cr2O7 ions to be adsorbed on
adsorption sites [67]. Maximum adsorption was observed at 500 mg/dm3 i.e.
98.05%. It can be observed that removal efficiency of the adsorbents generally
increased with increasing the quantity. It is due to the availability of
exchangeable sites for the adsorbate [82].
ADSORBENTS
Chapter 2
60
2.4.5 Effect of agitation speed

The agitation speed for the removal of Cr(VI) was varied from 50 rpm
to 200 rpm (Table 2.6), by keeping all other conditions constant (Fig. 2.7). The
removal of Cr(VI) was quantitative from 140 rpm. Cr(VI) removal efficiency
of WASAC generally increased with increasing agitation speed. The Cr(VI)
removal efficiency of WASAC increased from 76.37 to 98.05% when the
agitation speed increased from 90 to 140 rpm. The Cr(VI) removal efficiency
of the adsorbent remained constant for a higher agitation speed, due to the fact
that a higher agitation speed increases the degree of physicochemical
interaction between negatively charged surface of WASAC and metal ion at
acidic conditions, resulting in a higher Cr(VI) removal efficiency. An optimum
agitation speed is essentially required to maximize the interactions between
metal ions and adsorption sites of adsorbent in the solution [93].
2.4.6 Adsorption isotherm
Adsorption isotherms, which are the presentations of the amount of
solute adsorbed per unit of adsorbent, as a function of equilibrium
concentration in bulk solution at constant temperature were studied (Table 2.7).
If a quantity, q, of adsorbate is adsorbed by a porous solid adsorbent at constant
temperature and the steady state equilibrium concentration, then the function q
describes the adsorption isotherm. Figure 2.8 shows the adsorption isotherm for
the Cr(VI) adsorption on WASAC. The isotherm rises in the initial stages with
higher slope at low Ce and qe values. This indicates that, initially, there are
numerous readily accessible sites. At higher Ce values, a plateau occurs. This
confirms the monolayer coverage of Cr(VI) onto activated carbon particles
[11]. A variety of isotherm equations have been in use, some of which have a
theoretical foundation and some being of mere empirical nature. In the present
work, Langmuir and Freundlich isotherm has been tested.
ADSORBENTS
Chapter 2
61
2.4.7 Langmuir isotherm

A basic assumption of the Langmuir theory is that sorption takes place
at specific homogeneous sites within the adsorbent. It is then assumed that once
a metal ion occupies a site, no further sorption can take place at that site. The
rate of sorption to the surface should be proportional to a driving force
multiplied by area. The driving force is the concentration in the solution, and
the area is the amount of bare surface. If the fraction of covered surface is ,
the rate per unit of surface is:
ra = kL Ce (1 )
(5)
The desorption from the surface is proportional to the amount of surface

covered:
rd = kd
(6)
Where kL and kd are rate coefficients for adsorption and desorption, ra is

adsorption rate, rd is desorption rate, Ce is concentration in the solution, is
fraction of the surface covered and (1-) is uncovered surface area. At
equilibrium, the two rates are equal, and:
ra = rd
(7)
kL(1- ) Ce = kd
(8)
kL Ce- kLCe = kd
(9)
k L Ce = k d + k L Ce
(10)
kL = (kd + kL Ce)
(11)
k LC e
k d +k LC e
(12)
and
ADSORBENTS
Chapter 2
62
ka=
Since,
kL
kd
(13)
qe ,
qe
qm
qe = qm
(14)
(15)
Putting Eq. (12) in Eq. (15)
qe=
qmkLCe
kd+kLCe
(16)
Dividing Eq. (16) by kd
qe=
qmCekL/kd
kd/kd+CekL/kd
(17)
The saturated monolayer sorption capacity, qm, can be obtained. When

approaches 1, then qe = qm
The saturated monolayer isotherm can be represented as:
qmKLCe
1+ KLCe
(18)
qe
qmKL
Ce 1+KLCe
(19)
qe=
where, KL = kL / kd
Inverting Eq. (19), we get
Ce
1
KLCe
=
+
qe qmKL KLqm
(20)
ADSORBENTS
Chapter 2
63
The above Eq. (19) can be rearranged to the following linear form:
Ce
1
Ce
=
+
qe qmKL qm
(21)
where, Ce is the equilibrium concentration (mg/dm3); qe is the amount of metal

ion adsorbed (mg/g); qm is qe for a complete monolayer (mg/g); KL is sorption
equilibrium constant (dm3/mg). A plot of Ce/qe versus Ce (Fig. 2.9, Table 2.8)
should indicate a straight line of slope 1/qm and an intercept of 1/KLqm [102,
103].
A further analysis of the Langmuir equation can be made on the basis of
a dimensionless equilibrium parameter, RL [104] also known as the separation
factor, given by
RL=1 / (1+KLCe)
(22)
The value of RL lies between 0 and 1 for favorable adsorption, while RL> 1
represents unfavorable adsorption, and RL= 1 represents linear adsorption while
the adsorption process is irreversible if RL = 0.
The adsorption of Cr(VI) on WASAC follows the Langmuir isotherm
model for metal adsorption. The values of qm and KL were evaluated (Table
2.9). The dimensionless parameter RL between 0.016 to 0.364 is consistent with
the requirement for favorable adsorption. The high value of correlation
coefficient R2 indicates a good agreement between the parameters and confirms
the monolayer adsorption of Cr(VI) onto the adsorbent surface.
2.4.8 Freundlich isotherm
Freundlich isotherm assumes that the uptakes of metal ions occur on a
heterogeneous surface by multilayer adsorption and that the amount of
adsorbate adsorbed increases infinitely with an increase in concentration. It is a
most popular model for a single solute system, based on the distribution of
ADSORBENTS
Chapter 2
64
solute between the solid phase and aqueous phase at equilibrium [105]. The
Freundlich equation is expressed as
qe = Kf Ce1/n
(23)
where, Kf is the measure of adsorption capacity and n is the adsorption

intensity. Linear form of Freundlich equation [93] is,
log qe = log Kf + 1/n log Ce
(24)
where, qe is the amount adsorbed (mg/g), Ce is the equilibrium concentration of

adsorbate (mg/dm3) and Kf and n are the Freundlich constants related to the
adsorption capacity and adsorption intensity, respectively. A plot of log qe vs
log Ce (Fig. 2.10) from values in Table 2.10 gives a linear trace with a slope of
1/n and intercept of log Kf and the results are given in Table 2.11. When 1/n is
>1.0, the change in adsorbed metal ion concentration is greater than the change
in the metal ion concentration in solution. It is often found that the Freundlich
equation is fitted well to data at higher and intermediate concentrations, since
the Freundlich equation does not approach Henrys Law of ideal dilute
2
solutions [105]. The value of the correlation coefficient, R , obtained in this

case indicates that the Freundlich model gave a poorer fit to the experimental
data than the Langmuir isotherm model.
2.4.9 Adsorption kinetics
Samples of WASAC were agitated at 140 rpm with a fixed
concentration of adsorbate and the volume of solution was 50 mL at 299 2 K
in a thermostat. The adsorbent was introduced to the reaction flask and Cr(VI)
concentration, for each time interval from 0 min to 180 min was determined
spectrophotometrically.
ADSORBENTS
Chapter 2
65
Several kinetic models are in use to explain the mechanism of the

adsorption processes. A simple pseudo-first order equation was used
dqt / dt = k1(qeqt)2
(25)
where, qe and qt are the amount of adsorption at equilibrium and at time t (min)
respectively, and k1 is the rate constant of the pseudo-first order adsorption
process [106, 107]. Lagergren plot for the adsorption of Cr(VI) by WASAC for
adsorbent dosage, 0.5 g/dm3; concentration, 90 mg/dm3; initial pH, 2.0; and
temperature, 299 2 K. The log of the initial condition of qt = 0 at t = 0,
becomes easy for graphical presentation:
log(qe qt) = log qe k1t / 2.303
(26)
Plot of log (qe qt) vs. t (Fig. 2.11, Table 2.12) gives a straight line for first
order adsorption kinetics, which allow computation of the adsorption rate
constant, k1. The k1 and qe value for the initial concentration of 90 mg/dm3 are
found to be 1.04x103 min1 and 9.77 mg/g. The true value of qe obtained from
experiments is 8.83 mg/g. The value R2 was 0.967 for pseudo first order so
tried for pseudo second order.
The corresponding pseudo-second order rate equation [108] is given as,
t
1
1
t
2
qt
qe
k 2 qe
(27)
where, k2 is the rate constant for the pseudo-second order adsorption process.
The rate parameters k and qe can be directly obtained from the intercept and
slope of the plot of t/qt vs. t (Fig. 2.12). The values of rate constant k1 and k2
obtained graphically for both adsorption models are listed in Table 2.14. The
results show that the pseudo-first order model provided a better approximation
to the experimental kinetic data than the pseudo-second order model.
ADSORBENTS
Chapter 2
66
2.4.10 Intraparticle diffusion study

The possibility of intraparticle diffusion was explored by using an
intraparticle diffusion model. It is of major concern because it is ratedetermining step in the liquid adsorption systems. The intraparticle diffusion
varies with square root of time and is given [108, 86] as,
qt = kid t1/2 + c
(28)
where, c is constant and kid is the intraparticle diffusion rate constant (mg/g
min1/2), qt is the amount adsorbed at a time (mg/g), t is the time (min). The
intraparticle diffusion rate constant was determined from the slope of the linear
gradients of the plot qt versus t1/2 as shown in Fig. 2.13 (Table 2.15). The rate
constant of intraparticle diffusion at different temperatures is shown in Table
2.16. The intraparticle diffusion process is controlled by the diffusion of ions
within the adsorbent.
The mechanism of solute transfer to the solid includes diffusion through
the fluid film around the adsorbent particle and diffusion through the pores to
the internal adsorption sites. Initially the concentration gradient between the
film and the solid surface is large, and hence the transfer of solute onto the
solid surface is faster. That is why it takes lesser time to attain percentage
removal of Cr(VI) up to 74.95%. As time increases, intraparticle diffusion
becomes predominant. Hence solute takes more time to transfer from solid
surface to internal adsorption sites through the pores [74].
2.4.11 Adsorption thermodynamics
The thermodynamics of an adsorption process is obtained from a study
of the influence of temperature on the process. Temperature effect has been
studied for the adsorption of Cr(VI) ions by WASAC. It has been found that
the adsorption capacity increased from 13.98 mg/g to 19.78 mg/g (Fig. 2.14,
Table 2.17) as the temperature was increased from 303 K to 323 K at Cr(VI)
ion concentration of 200 mg/dm3, pH 2.0 and the other conditions were kept
ADSORBENTS
Chapter 2
67
constant. This indicates that the adsorption reaction was endothermic in nature.
The enhancement in the adsorption capacity may be due to the chemical
interaction between adsorbate and adsorbent, creation of some new adsorption
sites or the increased rate of intraparticle diffusion of Cr(VI) ions into the pores
of the adsorbent at higher temperatures [86].
The standard Gibbs energy was,
G = RT ln Kc
(29)
The equilibrium constants Kc was evaluated at each temperature using the

following relationship,
Kc = CAe /Ce
(30)
where, CAe is the amount adsorbed on solid phase at equilibrium and Ce is the
equilibrium concentration.
Other thermodynamic parameters such as change in standard enthalpy
(H) and standard entropy (S) were determined using the following
equations [11]
lnKc = S/RH/RT
(31)
H and S were obtained from the slope and intercept of the Vant Hoffs
plot of ln kc versus 1/T as shown in Fig. 2.15 (Table 2.18), positive value of
H indicates that the adsorption process is endothermic. The negative values
of G reflect the feasibility of the process and the values become more
negative with increase in temperature. Standard entropy determines the
disorderliness of the adsorption at solidliquid interface. Thermodynamic
parameters are summarized in Table 2.19. The positive value of S shows that
increasing randomness at the solid/liquid interface during the adsorption of
Cr(VI) ions on WASAC.
ADSORBENTS
Chapter 2
68
2.5 COMPARISON OF ADSORPTION CAPACITY OF WASAC WITH

OTHER ADSORBENT
A comparison was made, in term of adsorption capacity (qm) of
WASAC with other adsorbents (Table 2.20). The present study shows that
WASAC is an effective low-cost adsorbent for the removal of Cr(VI) from
aqueous solutions. It was observed that a pH of 2.0 was found to be an
optimum for adsorption of Cr(VI) in nearly all cases.
2.6 CONCLUSIONS
1) Limonia acidissima (wood apple) shell is a waste product which is
converted into a carbonaceous adsorbent and used for the removal Cr(VI)
ions from aqueous solution.
2) Characterization of the adsorbent showed that it was porous and very
effective in the removal of Cr(VI) ions from waste water.
3) The removal of Cr(VI) ions with an initial concentration 90 mg/g was found
to be 98.05% after shaking for 180 min at 140 rpm and at constant
temperature.
4) The increase in the adsorption capacity observed with increasing
temperature showed that the adsorption process was chemical in nature,
being feasible, spontaneous and endothermic as confirmed by the evaluation
of the relevant thermodynamic parameters, viz. H0, G0 and S0.
5) The experimental data for the adsorption process were well fitted by the
Langmuir adsorption isotherm model relative to the fit of the Freundlich
adsorption model. The Langmuir adsorption capacity was determined as
13.74 mg/g for Cr(VI) adsorption.
6) The adsorption of Cr(VI) ions obeyed the pseudo-first-order kinetic
equation which had 9.77 mg/g equilibrium adsorption capacity.
7) The ready availability of wood apple shell and the ease with which the
corresponding activated carbon may be produced favours its use as a means
of effectively removing Cr(VI) ions from aqueous solution.
ADSORBENTS
Chapter 2
69
Table 2.1
Elemental analysis and properties of WASAC
Property
Result
Ash content
8.12%
Bulk density
0.734 g/cm3
Moisture content
8.85%
Carbon
65.10%
Hydrogen
4.60%
Nitrogen
0.04%
Sulphur
2.35%
ADSORBENTS
Chapter 2
70
Table 2.2
Effect of pH on removal of Cr(VI), % and amount adsorbed, mg/g
Cr(VI)=90 mg/dm3, Time = 180 min. T= 299 2 K, WASAC= 500 mg,
Agitation speed = 140 rpm
pH
Amount adsorbed, q mg/g
Removal of Cr(VI), %
8.81
97.9
8.83
98.05
8.78
97.7
7.27
80.8
6.97
77.4
5.17
57.4
4.95
55.0
3.32
36.8
2.38
26.4
10
2.02
22.4
11
1.86
20.6
ADSORBENTS
Chapter 2
71
Table 2.3
Effect of shaking period on removal of Cr(VI), % and amount adsorbed, mg/g
Cr(VI) = 90 mg/dm3, pH=2, T= 299 2 K, WASAC =500 mg, Agitation speed
= 140 rpm
Time, min
Amount adsorbed, qt mg/g
15
3.54
39.28
30
4.13
45.80
45
5.08
56.53
60
6.04
67.10
75
6.75
74.95
90
7.27
80.81
105
7.95
88.27
120
8.39
93.27
135
8.49
94.27
150
8.60
95.61
165
8.79
97.75
180
8.83
98.05
210
8.83
98.05
ADSORBENTS
Chapter 2
72
Table 2.4
Effect of initial concentration of Cr(VI) on amount adsorbed, mg/g of Cr(VI)
and removal, % on WASAC
Time =180 min, pH=2, T= 299 2 K, WASAC=500 mg, Agitation speed =
140 rpm
Initial Conc. Cr(VI),
Amount adsorbed,
mg/dm3
q mg/g
90
8.83
98.05
100
9.78
97.75
110
10.62
96.60
120
11.23
93.60
130
11.62
89.40
140
12.08
86.60
150
12.75
84..23
160
13.19
82.43
170
13.42
78.94
180
13.70
76.11
190
13.87
72.68
200
13.94
69.7
ADSORBENTS
Chapter 2
73
Table 2.5
Effect of adsorbent dosage on Cr(VI) removal, % and amount adsorbed, mg/g
Cr(VI) = 90, Time= 180min, pH=2, T= 299 2 K, Agitation speed = 140 rpm
WASAC, mg
200
1.71
19.92
225
2.04
22.63
250
2.68
29.81
275
3.30
36.72
300
4.00
44.50
325
5.21
57.91
350
6.14
68.24
375
6.49
72.14
400
7.09
78.82
425
7.98
88.73
450
8.72
96.9
475
8.78
97.5
500
8.83
98.05
ADSORBENTS
Chapter 2
74
Table 2.6
Effect on agitating speed on removal of Cr(VI), % and amount adsorbed, mg/g
Cr(VI)=90 mg/dm3, Time= 180 min. T= 299 2 K, WASAC= 500 mg, pH=2
Agitation speed,
Amount adsorbed,
Removal of Cr(VI),
rpm
q mg/g
50
3.73
41.48
70
5.20
57.81
100
6.87
76.37
120
8.45
93.78
140
8.83
98.05
160
8.83
98.05
180
8.82
98.00
200
8.83
98.05
ADSORBENTS
Chapter 2
75
Table 2.7
Adsorption isotherm for Cr(VI) adsorption on WASAC
Time= 180 min, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed =
140 rpm
Ce
1.75
8.83
2.25
9.78
3.74
10.62
7.68
11.23
13.78
11.62
19.52
12.08
22.75
12.75
28.1
13.16
35.8
13.42
43.00
13.70
51.9
13.87
60.59
13.94
ADSORBENTS
Chapter 2
76
Table 2.8
Langmuir isotherm for adsorption of Cr(VI) on WASAC
140 rpm
Ce
Ce/q
1.75
0.19
2.25
0.23
3.74
0.35
7.68
0.68
13.78
1.19
19.52
1.61
22.75
1.79
28.10
2.13
35.80
2.67
43.00
3.76
51.90
3.76
60.59
4.67
Table 2.9
Langmuir constant for the adsorption of Cr(VI) on WASAC
qm (mg/g)
KL(1/mg)
R2
13.74
0.999
0.998
ADSORBENTS
Chapter 2
77
Table 2.10
Freundlich adsorption isotherm for Cr(VI) on WASAC
140 rpm
log Ce
log qe
0.24
0.95
0.31
0.99
0.57
1.02
0.88
1.05
1.14
1.07
1.29
1.08
1.36
1.11
1.44
1.12
1.49
1.13
4.63
1.14
1.72
1.14
1.78
1.15
Table 2.11
Freundlich constant for the adsorption of Cr(VI) on WASAC
Kf
R2
8.72
8.42
0.969
ADSORBENTS
Chapter 2
78
Table 2.12
Pseudo first order for Cr(VI) adsorption on WASAC
Cr(VI)=90 mg/dm3, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed
= 140 rpm
t (min)
log (qe-qt)
0.95
15
0.72
30
0.67
45
0.57
60
0.45
75
0.32
90
0.19
105
-0.05
120
-0.36
135
-0.47
150
-0.64
ADSORBENTS
Chapter 2
79
Table 2.13
Pseudo second order for Cr(VI) adsorption on WASAC
= 140 rpm
t
t/qt
15
4.24
30
7.26
45
8.86
60
9.94
75
11.11
90
12.37
105
13.20
120
14.30
135
15.90
150
17.44
165
18.77
180
20.41
Table 2.14
Kinetic Parameters for the adsorption of Cr(VI) onto WASAC
pseudo first order
qe exp.
k1x103
qe calc.
(mg/g)
(min1)
(mg/g)
8.83
1.04
9.77
pseudo second order

R2
k2 x103
qe calc.
R2
(mg/g)
0.9671
0.031
11.24
0.9881
ADSORBENTS
Chapter 2
80
Table 2.15
Intraparticle diffusion plot for adsorption of Cr(VI) on WASAC
= 140 rpm
t 0.5
qt
3.87
3.54
5.48
4.43
6.71
5.08
7.75
6.04
8.66
6.75
9.49
7.27
10.25
7.95
10.95
8.39
11.62
8.49
12.23
8.60
Table 2.16
Study of Intraparticle Diffusion of adsorption of Cr(VI) on WASAC
kid
R2
(mg g1min1)
0.698
0.9812
ADSORBENTS
Chapter 2
81
Table 2.17
Effect of temperature on amount adsorbed of Cr(VI) on WASAC
Cr(VI)=200 mg/dm3, Time= 180 min, WASAC= 500 mg, pH=2, Agitation
speed = 140 rpm
TK
303
13.98
308
16.84
313
18.14
318
18.96
323
19.78
ADSORBENTS
Chapter 2
82
Table 2.18
Van't Hoff plots for adsorption of Cr(VI) on WASAC
speed = 140 rpm
1/T
lnKc
0.00330
0.44
0.00324
0.63
0.00319
0.70
0.00314
0.75
0.00309
0.79
Table 2.19
Thermodynamic parameters of adsorption of Cr(VI) on WASAC
T, K
G, kJ/mol
303
-1.110
308
-1.604
313
-1.824
318
-1.971
323
-2.115
H, kJ/mol
S, J/(mol k)
1.582
5.707
ADSORBENTS
Chapter 2
83
Table 2.20
Comparison of adsorption capacity of WASAC with other Adsorbents
Adsorbent
qm, mg/g
Reference
Acid modified waste activated carbon
10.929
[5]
River sand
0.15
[17]
Manganese-coated sand
6.27
[18]
Short chain polyaniline (PANI)
62.9
[28]
Zeolite NaX
6.414
[37]
Kaolinite
11.6
[38]
Acid-activated kaolinite
13.9
[38]
Poly(oxozirconium) kaolinite
10.9
[38]
TBA-kaolinite,
10.6
[38]
Fly ash
0.266
[53]
Turkish Afsin-Elbistan fly ash
0.1489
[54]
Seyitomer fly ash
0.0162
[54]
Bagasse fly ash
4.35
[55]
Coal fly ash
18.28
[56]
Beech (Fagus orientalis L.) sawdust
16.13
[63]
Wheat bran
0.942
[66]
Wheat bran
0.942
[67]
Pre-boiled sunflower stem
4.9
[71]
Formaldehyde treated sunflower stem
3.6
[71]
17.27
[81]
Bael fruit (Aegle marmelos correa)

shell
[81]
Sulfuric acid treated Groundnut husk
7.01
[82]
Silver nitrate impregnate
11.4
[82]
Oak saw dust
1.72
[87]
Coconut tree saw dust
3.46
[88]
Indigenous waste
12.57
[90]
Coconut shell carbon
10.88
[93]
ADSORBENTS
Chapter 2
84
Rice husk
0.8
[94]
Waste biogas slurry
5.87
[95]
Indian Rosewood sawdust
10.00
[96]
Ficus religiosa leaves
5.66
[97]
Sago waste
5.78
[98]
Sal (Shorea robusta)
9.55
[99]
Wood apple shell
13.74
Present work
ADSORBENTS
Chapter 2
85
Fig. 2.1
FTIR spectrum of WASAC
ADSORBENTS
Chapter 2
86
2.2 (a)
SEM image of WASAC adsorbent
2.2 (b)
ADSORBENTS
Chapter 2
87
2.2 (c)
ADSORBENTS
Chapter 2
100
80
60
40
20
10
0
10
Amount adsorbed of Cr(VI), mg/g
88
12
pH
Fig. 2.3
Effect of pH on removal of Cr(VI), % and amount adsorbed, mg/g
Cr(VI)=90 mg/dm3, Time = 180 min, T= 299 2 K, WASAC = 500 mg,
Agitation speed = 140 rpm
ADSORBENTS
Chapter 2
100
80
60
40
20
0
0
50
100
150
200
89
10
250
time, min
Fig. 2.4
Effect of shaking period on removal of Cr (VI), % and amount adsorbed, mg/g
Cr(VI) = 90 mg/dm3, pH=2, T= 299 2 K, WASAC=500 mg, Agitation speed
= 140 rpm
ADSORBENTS
Chapter 2
90
100
80
10
60
40
5
20
0
80
120
160
200
15
0
240
Initial conc. of Cr(VI), mg/dm
Fig. 2.5
Effect of initial concentration on amount adsorbed, mg/g and removal, % of
Cr(VI)
Time= 180min, pH=2, T= 299 2 K, WASAC=500 mg, Agitation speed = 140
rpm
ADSORBENTS
Chapter 2
100
80
60
40
20
0
150
91
10
250
350
450
550
Adsorbent, mg
Fig. 2.6
Effect of adsorbent dosage on Cr(VI) removal, % and amount adsorbed, mg/g
Cr(VI) = 90, Time =180min, pH=2, T= 299 2K, Agitation speed = 140 rpm
ADSORBENTS
Chapter 2
100
80
60
40
20
Amount adsorbed of Cr (VI), mg/g
92
10
0
50
100
150
200
250
rpm
Fig. 2.7
Effect on agitating speed on removal of Cr(VI), % and amount adsorbed, mg/g
Cr(VI)=90 mg/dm3, Time= 180 min, T= 299 2 K, WASAC= 500 mg, pH=2
ADSORBENTS
Chapter 2
93
14
12
qe mg/g
10
8
6
4
2
0
0
20
40
60
80
Ce mg/dm
Fig. 2.8
Adsorption isotherm for Cr(VI) adsorption on WASAC
Time = 180 min, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed =
140 rpm
ADSORBENTS
Chapter 2
94
5
4
Ce /qe
3
2
1
0
0
20
40
60
80
Ce
Fig. 2.9
Langmuir isotherm for adsorption of Cr(VI) on WASAC
140 rpm
ADSORBENTS
Chapter 2
95
1.2
1.1
1
log qe
0.9
0.8
0.7
0.6
0.5
0
0.5
1.5
log Ce
Fig. 2.10
Freundlich adsorption isotherm for Cr(VI) on WASAC
140 rpm
ADSORBENTS
Chapter 2
96
1
0.8
0.6
log (qe-qt)
0.4
0.2
0
0
50
100
150
200
-0.2
t min
-0.4
-0.6
-0.8
Fig. 2.11
Pseudo first order for adsorption of Cr(VI) on WASAC
Cr(VI) =90 mg/dm3, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed
= 140 rpm
ADSORBENTS
Chapter 2
97
25
20
t/qt
15
10
0
0
50
100
150
200
t, min
Fig. 2.12
Pseudo second order for Cr(VI) on WASAC
Cr(VI) = 90 mg/dm3, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed
= 140 rpm
ADSORBENTS
Chapter 2
98
10
qt (mg/g)
8
6
4
2
0
2
1/2
10
12
Fig. 2.13
Intraparticle diffusion plot for adsorption of Cr(VI) on WASAC
Cr(VI) = 90 mg/dm3, T= 299 2 K, WASAC= 500 mg, pH=2, Agitation speed
= 140 rpm
ADSORBENTS
Chapter 2
99
25
qe (mg/g)
20
15
10
0
300
305
310
315
320
325
T (K)
Fig. 2.14
Effect of temperature on amount adsorbed of Cr(VI) on WASAC
speed = 140 rpm
ADSORBENTS
Chapter 2
100
lnKc
0.8
0.6
0.4
0.2
0
0.00305
0.0031
0.00315
0.0032
0.00325
0.0033
0.00335
1/T (K)
Fig. 2.15
Van't Hoff plots for adsorption of Cr(VI) on WASAC
Cr(VI) =200 mg/dm3, Time= 180 min, WASAC= 500 mg, pH=2, Agitation
speed = 140 rpm
ADSORBENTS
Chapter 2
101
References
[1]
F. Gholami, A. H.Mahvi, Gh. A.Omrani, S.Nazmara, A. Ghasri,

Removal of chromium (VI) from aqueous solution by ulmus leaves,
Iran. J. Environ. Health. Sci. Eng. 3 (2006) 97-102.
[2]
K. O. Olayinka, B. I. Alo, T. Adu, Sorption of heavy metals from

electroplating effluents by low cost adsorbents II: Use of waste tea,
coconut shell and coconut husk, J. Appl. Sci. 7 (2007) 2307-2313.
[3]
A. Saravanan, V. Brindha, R. Manimekalai, S. Krishnan, An evaluation

of chromium and zinc biosorption by a sea weed (Sargassum sp.) under
optimized conditions, Ind. J. Sci. Technol. 2 (2009) 53-56.
[4]
N. Tazrouti, M. Amrani, Chromium (VI) adsorption onto activated

sulfate lignin, Wat. Pract. Technol. 4 (2009) 1-13.
[5]
P. K.Ghosh, Hexavalent chromium [Cr(VI)] removal by acid modified

waste activated carbons, J. Hazard. Mater. 171 (2009) 116-122.
[6]
M. P. Candela, J. M.Martinez, R. T. Macia, Chromium removal with

activated carbons, Wat. Res. 29 (1995) 2174-2180.
[7]
IARC, Monographs on the evolution of the carcinogenetic risk of

chemical to humans, Supplement 4, World Health Organization:
Geneva, Switzerland (1982).
[8]
I. Bhatti, K. Qureshi, R.A. Kazi, A.K. Ansari, Preparation and

characterization of chemically activated almond shells by optimization
of adsorption parameters for removal of chromium VI from aqueous
solutions. World Acad. Sci. Eng. Technol. 34 (2007) 199-204.
[9]
V. Sarin, K.K. Pant, Removal of chromium from industrial waste by

using eucalyptus bark. Bioresource Technol. 97 (2006) 15-20.
[10]
E. Demirbas, M. Kobyab, E. Senturk, T. Ozkan, Adsorption kinetics for

the removal of chromium (VI) from aqueous solutions on the activated
carbons prepared from agricultural wastes, Water S. A. 30 (2004) 533540.
[11]
H. Demiral, I. Demiral, F. Tumsek, B. Karabacakoglu, Adsorption of

chromium (VI) from aqueous solution by activated carbon derived from
ADSORBENTS
Chapter 2
102
olive bagasse and applicability of different adsorption models, Chem.

Eng. J. 144 (2008) 188-196.
[12]
Z. Hu, L. Lei, Li. Yijiu, Y. Ni, Chromium adsorption on highperformance activated carbons from aqueous solution, Sep .Purif.
Technol. 31 (2003) 13-18.
[13]
V. K. Gupta, A.Rastogi, A. Nayak, Adsorption studies on the removal of

hexavalent chromium from aqueous solution using a low cost fertilizer
industry waste material, J. Colloid Interf. Sci. 342 (2010) 135- 141.
[14]
L. Monser, N. Adhoum, Modified activated carbon for the removal of

copper, zinc, chromium and cyanide from wastewater, Sep. Purif.
Technol. 26 (2002) 137-146.
[15]
Y. Jiang, Y. Wu, J. Liu, X. Xia, D. Wang, Ammonium

pyrrolidinedithiocarbamate modified activated carbon
micro-column
extraction for the determination of As(III) in water by graphite furnace

atomic absorption spectrometry, Microchim Acta 161 (2008) 137-142.
[16]
T.
Madrakian,
A.
Afkhami,
A.
Esmaeili,
Spectrophotometric
determination of bismuth in water samples after preconcentration of its

thiourea-bromide ternary complex on activated carbon, Talanta 60
(2003) 831-838 .
[17]
Y.C. Sharma, C.H. Weng, Removal of chromium (VI) from water and
wastewater by using riverbed sand: Kinetic and equilibrium studies, J.
Hazard. Mater. 142 (2007) 449454.
[18]
S. M. Lee, W.G. Kim, C. Laldawngliana, D. Tiwari, Removal Behavior

of Surface Modified Sand for Cd(II) and Cr(VI) from Aqueous
Solutions, J. Chem. Eng. Data 55 (2010) 30893094.
[19]
H. Katsumata, S. Kaneco, K. Inomata, K. Itoh, K. Funasaka,

.Masuyama, T. Suzuki, K. Ohta, Removal of heavy metals in rinsing
wastewater from plating factory by adsorption with economical viable
materials, J. Environ. Manage. 69 (2003) 187191.
[20]
D. Gang, S. K. Banerji, T. E. Clevenger, Factors affecting chromium

(VI) removal by modified poly(4-vinylpyridine) coated silica gel,
ADSORBENTS
Chapter 2
103
Practice Periodical of Hazard., Toxic, Radioactive Waste Manage. 5

(2001) 58-65.
[21]
P.Chowdhury, P.Mondal, K. Roy, Synthesis of polyaniline nanoparticle

grafted silica gel and study of its Cr(VI) binding property, J. Appl. Poly.
Sci. 119 (2011) 823-829.
[22]
P. Chowdhury, P. Mondal, K. Roy, Synthesis of cross-linked graft

copolymerfrom
chloride
[2-(methacryloyloxy)ethyl]
trimethylammonium
and poly(vinyl alcohol) for removing chromium(VI) from
aqueous solution, Polym. Bull. 64 (2010) 351362.

[23]
I.S. Ahamed, A.K. Ghonaim, A.A.A. Hakim, M. M. Moustafa, A.H.

K.El- Din, Synthesis and characterization of some polymers for
removing of some heavy metal ions of industrial wastewater, J. Appl.
Sci. Res. 4 (2008) 1946-1958.
[24]
M. R. Samani, S. M. Borghei, A. Olad, M. J. Chaichi, Removal of

chromium from aqueous solution using polyaniline Poly ethylene
glycol composite J. Hazard. Mater. 184 (2010) 248254.
[25]
V. Neagu, S. Mikhalovsky, Removal of hexavalent chromium by new

quaternized crosslinked poly(4-vinylpyridines) J. Hazard. Mater.183
(2010) 533540.
[26]
S. Deng, R. Bai, Removal of trivalent and hexavalent chromium with

aminated polyacrylonitrile fibers: performance and mechanisms, Wat.
Res. 38 (2004) 24242432.
[27]
Y. Nakano, K. Takeshita, T. Tsutsumi, Adsorption mechanism of

hexavalent chromium by redox within condensed-tannin gel, Wat. Res.
35 (2001) 496-500.
[28]
P. A. Kumar, S. Chakraborty, M. Ray, Removal and recovery of

chromium from wastewater using short chain polyaniline synthesized on
jute fiber, Chem. Eng. J. 141 (2008) 130140.
[29]
X. Hua, J.Wang, Y. Liua, X. Li, G. Zeng, Z. Bao, X. Zeng, A.Chen, F.

Long, Adsorption of chromium (VI) by ethylenediamine-modified
ADSORBENTS
Chapter 2
104
cross-linked
magnetic
chitosan
resin:
Isotherms,
kinetics
and
thermodynamics, J. Hazard. Mater. 185 (2011) 306314.

[30]
Y. Zeng, H. Woo, G. Lee, J. Park, Adsorption of Cr(VI) on

hexadecylpyridinium bromide (HDPB) modified natural zeolites,
Micropor. Mesopor. Mater. 130 (2010) 83-91.
[31]
V. Campos, L. C. Morais, P. M. Buchler, Removal of chromate from

aqueous solution using treated natural zeolite, Environ. Geol. 52 (2007)
15211525.
[32]
R. L.Ramos, A. J.Azuara, P.E. D.Flores, R.M. G.Coronado, J. M.

Barron,
M.S. B.Mendoza, Adsorption of chromium(VI) from an
aqueous solution on a surfactant-modified zeolite, Colloids and Surfaces

A: Physicochem. Eng. Aspects 330 (2008) 3541.
[33]
M. Noroozifar, M. K. Motlagh, M.N. Gorgij, H.R. Naderpour,

Adsorption behavior of Cr(VI) on modified natural zeolite by a new
bolaform
N,N,N,N,N,N-hexamethyl-1,9-nonanediammonium
dibromide reagent, J. Hazard. Mater. 155 (2008) 566-571.

[34]
Y. Orhan, S. Kocaoba, Adsorption of toxic metals by natural and

modified clinoptilolite, Annali di Chimica 97 (2007) 781-790.
[35]
S. Babel, T A Kurniawan, A research study on Cr(VI) removal from

contaminated wastewater using natural zeolite, J. Ion Exch.14 (2003)
289- 292.
[36]
M.A. Barakat, Adsorption of heavy metals from aqueous solution on

synthetic zeolite, Res. J. Environ. SCi. 2 (2008) 13-22.
[37]
P. K. Pandey, S. K. Sharma, S. S. Sambi, Kinetics and equilibrium study

of chromium adsorption on zeolite NaX, Int. J. Environ. Sci. Tech. 7
(2010) 395-404.
[38]
K. G. Bhattacharyya, S. Sen Gupta, Adsorption of Chromium (VI) from

Water by Clays, Ind. Eng. Chem. Res. 45 (2006) 7232-7240.
[39]
F. Gode, N. Ozturk,Y. Sert, S. Bahceli, Adsorption of Cr(VI) from

aqueous solutions onto raw and acid-activated resadiye and hancl
clays, Spectroscopy Let. 43 (2010) 6878.
ADSORBENTS
Chapter 2
[40]
105
S. Arfaoui, N. Frini-Srasra, E. Srasra, Modelling of the adsorption of the

chromium ion by modified clays, Desalination 222 (2008) 474481.
[41]
J. Hu, S.W. Wang, D.D. Shao, Y.H. Dong, J.X. Li, X.K. Wang,
Adsorption and reduction of chromium(VI) from aqueous solution by
multiwalled carbon nanotubes, Open Environ. Pollut. Toxicol. J. 1
(2009) 66 -73.
[42]
J. Hu, C. Chen, X. Zhu, X. Wang Removal of chromium from aqueous

solution by using oxidized multiwalled carbon nanotubes, J. Hazard.
Mater.162 (2009) 15421550.
[43]
K. Pillay, E.M. Cukrowskab, N.J. Coville, Multi-walled carbon

nanotubes as adsorbents for the removal of parts per billion levels of
hexavalent chromium from aqueous solution, J. Hazard. Mater. 166
(2009) 10671075.
[44]
H.J. Park, L. L. Tavlarides, Adsorption of chromium (VI) from aqueous

solutions using an imidazole functionalized adsorbent, Ind. Eng. Chem.
Res. 47 (2008) 3401-3409.
[45]
P. Yuan, M. Fan, D.Yang, H. He, D. Liu, A. Yuan, J. Zhu, T.H. Chen,

Montmorillonite-supported magnetite nanoparticles for the removal
of hexavalent chromium [Cr(VI)] from aqueous solutions, J. Hazard.
Mater. 166 (2009) 821829.
[46]
Y. A. Aydn, N. D. Aksoy, Adsorption of chromium on chitosan:

Optimization, kinetics and thermodynamics, Chem. Eng. J. 151 (2009)
188194.
[47]
P. Baroni, R.S. Vieira, E. Meneghetti, M.G.C. da Silva, M.M. Beppu

Evaluation of batch adsorption of chromium ions on natural and
crosslinked chitosan membranes, J. Hazard. Mater. 152 (2008) 1155
1163.
[48]
D. C. Sharma, C. F. Forster, Removal of hexavalent chromium using

sphagnum moss peat, Wat. Res. 27 (1993) 1201-1208.
[49]
G. Arslan, E. Pehlivan, Batch removal of chromium(VI) from aqueous

solution by Turkish brown coals, Bioresource Technol. 98 (2007) 2836
ADSORBENTS
Chapter 2
106
2845.
[50]
K. Selvaraj, S. Manonmani, S. Pattabhi, Removal of hexavalent

chromium using distillery sludge, Bioresource Technol. 89 (2003) 207
211.
[51]
V. K. Gupta, M. Gupta, S. Sharma, process development for the removal

of lead and chromium from aqueous solutions using red mud an
aluminium industry waste, Wat. Res. 35 (2001) 1125-1134.
[52]
E. Malkoc, Y. Nuhoglu, Potential of tea factory waste for chromium

(VI) removal from aqueous solutions: Thermodynamic and kinetic
studies, Sep. Purif. Technol. 54 (2007) 291298.
[53]
Y.C. Sharma, Uma, S.N. Upadhyay, C.H. Weng, Studies on an

economically viable remediation of chromium rich waters and
wastewaters by PTPS fly ash Colloids and Surfaces A: Physicochem.
Eng. Aspects 317 (2008) 222228.
[54]
B. Bayat, Comparative study of adsorption properties of Turkish fly

ashes II. The case of chromium (VI) and cadmium (II), J. Hazard. Mater.
B95 (2002) 275290.
[55]
V.K. Gupta, I. Ali, Removal of lead and chromium from wastewater

using bagasse fly asha sugar industry waste, J. Colloid Interf. Sci.
271 (2004) 321328.
[56]
W. Jianlong, Removal of Cr(VI) from aqueous solution by coal flyash

adsorption I: Characteristics of chromium adsorption on flyash, Toxicol.
Environ. Chem. 68 (1999) 53-62.
[57]
P. Sethuraman, N. Balasubramanian, Removal of Cr(VI) from aqueous

solution
using
Bacillus
subtilis,
Pseudomonas
aeruginosa
and
Enterobacter cloacae, Int. J. Eng. Sci. Technol. 2 (2010) 1811-1825.

[58]
K. Tarangini, A. Kumar,G. R. Satpathy,V. K. Sangal, Statistical

optimization of process parameters for Cr(VI) biosorption onto mixed
cultures of pseudomonas aeruginosa and bacillus subtilis, Clean Soil,
Air, Water 37 (2009) 319 327.
ADSORBENTS
Chapter 2
[59]
107
C. Quintelas, Z. Rocha, B. Silva, B. Fonseca, H. Figueiredo, T. Tavares,

Removal of Cd(II), Cr(VI), Fe(III) and Ni(II) from aqueous solutions by
an E. coli biofilm supported on kaolin, Chem. Eng. J. 149 (2009) 319
324.
[60]
S. Srivastava, I. S. Thakur, Isolation and process parameter optimization

of Aspergillus sp.for removal of chromium from tannery effluent,
Bioresource Technol. 97 (2006) 11671173.
[61]
V. Vinodhini, N. Das, Mechanism of Cr(VI) biosorption by neem

sawdust, Am-Euras. J. Sci. Res. 4 (2009) 324-329.
[62]
D. Sarkar, S. K. Das, P. Mukherjee, A. Bandyopadhyay, Proposed

adsorptiondiffusion model for characterizing chromium(VI) removal
using dried water hyacinth roots, Clean Soil, Air, Water 38 (2010)
764770.
[63]
F.N. Acar, E. Malkoc, The removal of chromium (VI) from aqueous

solutions by Fagus orientalis L., Biores. Technol. 94 (2004) 1315.
[64]
E. Pehlivan, T. Altun, Biosorption of chromium (VI) ion from aqueous

solutions using walnut, hazelnut and almond shell, J. Hazard. Mater. 155
(2008) 378384.
[65]
D. Park, S. R. Lim, Y. S. Yun, J. M. Park, Reliable evidences that the

removal mechanism of hexavalent chromium by natural biomaterials is
adsorption-coupled reduction, Chemosphere 70 (2007) 298305.
[66]
G. H. Pino, L. M. S. de Mesquita, M. L. Torem, Biosorption of heavy

metals by powder of green coconut shell, Sep. Sci. Technol. 41(2006)
31413153.
[67]
M. Nameni, M. R. A. Moghadam, M. Arami, Adsorption of hexavalent

chromium from aqueous solutions by wheat bran, Int. J. Environ. Sci.
Technol. 5 (2008) 161-168.
[68]
E.A. Oliveira, S.F. Montanher, A.D. Andrade, J.A. Nobreg, M.C.

Rollemberg, Equilibrium studies for the sorption of chromium and
nickel from aqueous solutions using raw rice bran, Process Biochem. 40
(2005) 34853490.
ADSORBENTS
Chapter 2
[69]
108
S. Dhanakumar, G. Solaraj, R. Mohanraj, S. Pattabhi, Removal of

Cr(VI) from aqueous solution by adsorption using cooked tea dust, Ind.
J. Sci. Technol. 1(2007) 1-6.
[70]
M. A, Abdullah, A.G. D. Prasad, Kinetic and equilibrium studies for the

biosorption of Cr(VI) from aqueous solutions by potato peel waste,
Int. J. Chem. Eng. Res. 1(2009) 5162.
[71]
M. Jain, V.K. Garg, K. Kadirvelu, Chromium(VI) removal from

aqueous system using Helianthus annuus(sunflower) stem waste,
J.Hazard. Mater. 162 (2009) 365372.
[72]
N. Ahalya, T.V. Ramachandra, R.D. Kanamadi, Biosorption of Heavy

Metals, Res. J .Chem. Environ. 7 (2003) 1-16.
[73]
A. Sharma, K. G. Bhattacharyya, Adsorption of chromium (VI) on

Azadirachta Indica (neem) leaf powder, Adsorption 10 (2004) 327338.
[74]
B.V. Babu, S. Gupta, Adsorption of Cr(VI) using activated neem

leaves: kinetic studies, Adsorption 14 (2008) 8592.
[75]
D. Kratochvil, P. Pimentel, B. Volesky, Removal of trivalent and

hexavalent Chromium by seaweed biosorbent, Environ. Sci. Technol.
32 (1998) 2693-2698.
[76]
M. Bansal, D.Singh, V.K. Garg, A comparative study for the removal

of hexavalent chromium from aqueous solution by agriculture wastes
carbons, J. Hazard. Mater. 171 (2009) 8392.
[77]
L. Dupont, E. Guillon, Removal of Hexavalent Chromium with a

Lignocellulosic Substrate Extracted from Wheat Bran, Environ. Sci.
Technol. 37 (2003) 4235-4241.
[78]
U. K. Garg, M.P. Kaur, D. Sud, V.K. Garg, Removal of hexavalent

chromium from aqueous solution by adsorption on treated sugarcane
bagasse using response surface methodological approach, Desalination
249 (2009) 475479.
[79]
F. Di Natale, A. Lancia, A. Molino, D. Musmarra, Removal of

chromium ions form aqueous solutions by adsorption on activated
carbon and char, J. Hazard. Mater. 145 (2007) 381390.
ADSORBENTS
Chapter 2
[80]
109
J. Fang, Z. Gu, D. Gang, C. Liu, E. Ilton, B. Deng, Cr(VI) Removal

from Aqueous Solution by Activated Carbon Coated with Quaternized
Poly (4- vinylpyridine), Environ. Sci. Technol. 41 (2007) 4748-4753.
[81] J. Anandkumar, B. Mandal, Removal of Cr(VI) from aqueous solution

using Bael fruit (Aegle marmelos correa) shell as an adsorbent, J.
Hazard. Mater. 168 (2009) 633640.
[82]
S. P. Dubey, K. Gopal, Adsorption of chromium (VI) on low cost

adsorbents derived from agricultural waste material: A comparative
study, J. Hazard. Mater. 145 (2007) 465470.
[83]
M. Bansal, D. Singh, V.K. Garg, A comparative study for the removal

of hexavalent chromium from aqueous solution by agriculture wastes
carbons, J. Hazard. Mater. 171 (2009) 8392.
[84]
M. Owlad, M. K. Aroua, W. M. A. W. Daud, Hexavalent chromium

adsorption on impregnated palm shell activated carbon with
polyethyleneimine, Bioresource Technol. 101 (2010) 50985103.
[85]
H. Zhang, Y. Tang, D. Cai, X. Liu, X. Wang, Q. Huang, Z. Yu,

Hexavalent chromium removal from aqueous solution by algal bloom
residue derived activated carbon: Equilibrium and kinetic studies, J.
Hazard. Mater. 181 (2010) 801808.
[86]
T. Karthikeyan, S. Rajgopal, L. R. Miranda, Chromium (VI) adsorption

from aqueous solution by Hevea Brasilinesis sawdust activated carbon,
J. Hazard. Mater. B124 (2005) 192199.
[87]
M. E. Argun, S. Dursun, C. Ozdemir, M. Karatas, Heavy metal

adsorption by modified oak sawdust: Thermodynamics and kinetics, J.
Hazard. Mater. 141 (2007) 7785.
[88]
K. Selvi, S. Pattabhi, K. Kadirvelu, Removal of Cr(VI) from aqueous

solution by adsorption onto activated carbon, Bioresource Technol. 80
(2001) 87-89.
[89]
S Arivoli, P.Martin, D. Prasath, M Thenkuzhali, Adsorption of

chromium ion by acid activated low cost carbon, EJEAFChe 6 (2007)
2323-2340.
ADSORBENTS
Chapter 2
[90]
110
X.S. Wang, L. F. Chen, K. L. Chen, W. Y. Wan, Y.J. Tang, Removal of

Cr(VI) with wheat-residue derived black carbon: Reaction mechanism
and adsorption performance, J. Hazard. Mater. 175 (2010) 816-822.
[91]
N.H. Hsu, S.L. Wang, Y.H. Liao, S.T. Huang, Y.M. Tzou, Y.M. Huang,
Removal of hexavalent chromium from acidic aqueous solutions using
rice straw-derived carbon, J. Hazard. Mater. 171 (2009) 10661070.
[92] D. Mohan, K. P. Singh, V. K. Singh, Removal of hexavalent chromium

from aqueous solution using low-cost activated carbons derived from
agricultural waste materials and activated carbon fabric cloth, Ind. Eng.
Chem. Res. 44 (2005) 1027-1042.
[93]
S. Babel, T. A. Kurniawan, Cr(VI) removal from synthetic wastewater

using coconut shell charcoal and commercial activated carbon modified
with oxidizing agents and/or chitosan, Chemosphere 54 (2004) 951967.
[94]
N. R. Bishnoi, M. Bajaj, N. Sharma, A. Gupta, Adsorption of Cr(VI) on

activated rice husk carbon and activated alumina, Bioresource Technol.
91 (2004) 305307.
[95]
C. Namasivayam and R.T.Yamuna, Adsorption of chromium (VI) by a

low-cost adsorbent: biogas residual slurry, Chemosphere 30 (1995)
561-578.
[96]
V.K. Garg, R. Gupta, R. Kumar, R.K. Gupta, Adsorption of chromium

from aqueous solution on treated sawdust, Bioresource Technol. 92
(2004) 7981.
[97]
S. Qaiser, A. R. Saleemi, M. M. Ahmad, Heavy metal uptake by agro

based waste materials, E. J. Biotechnol. 10 (2007) 409-416.
[98]
N. Vennilamani, K. Kadirvelu, Y. Sameena, S. Pattabhi, Utilization of

activated carbon prepared from industrial solid waste for the removal of
chromium(VI) ions from synthetic solution and industrial Effluent,
Adsorp. Sci. Technol. 23 (2005) 145-160.
[99]
S. S. Baral, S. N. Das, P. Rath, Hexavalent chromium removal from

aqueous solution by adsorption on treated sawdust, Biochem. Eng. J. 31
(2006) 216222.
ADSORBENTS
Chapter 2
111
[100] A. I. Vogel, A text book of Quantitative Inorganic Analysis including

Elemental Instrumental analysis, Edition 3rd, The English Language
Book Society and Longman, London, 1975.
[101] Z. Marczenko, Spectrophotometric Determination of Elements, Ellis
Horwood, Limited, Chinchester, 1976.
[102] I. Langmuir, The constitution and fundamental properties of solids and
liquids, J. Am. Chem. Soc. 38 (1916) 2221-2295.
[103] E.O. Aluyor, I.O. Oboh, K.O. Obahiagbon, Equilibrium sorption
isotherm for lead (Pb) ions on hydrogen peroxide modified rice hulls,
Int. J. Phys. Sci. 4 (2009) 423-427.
[104] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Pore and solid
diffusion kinetics in fixed bed adsorption under constant pattern
conditions, Ind. Eng. Chem. Fundam. 5 (1966) 212-223.
[105] P.Sivakumar, P.N.Palanisamy, Adsorption studies of basic red 29 by a
nonconventional activated carbon prepared from euphorbia antiquorum
L, Int. J. Chem Tech Res. 1(2009) 502-510.
[106] Y. S. Ho, G. McKay, The Sorption of Lead (II) ions on peat, Wat. Res.
33 (1999) 578-584,
[107] N. Ozturk, D. Kavak, Adsorption of boron from aqueous solutions
using fly ash: Batch and column studies, J. Hazard. Mater. B127 (2005)
8188.
[108] Y.S. Ho, G. McKay, Sorption of dye from aqueous solution by peat,
Chem. Eng. J. 70 (1998) 11.5-124.
ADSORBENTS

10 - Chapter 2 PDF

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

10 - Chapter 2 PDF

Diunggah oleh

Hak Cipta:

Format Tersedia

CHAPTER 2

Efficient adsorption of Cr (VI) from

Limonia acidissima (Wood apple)

Wood Apple Shell

modified with surfactant hexadecylpyridinium bromide was investigated which

tetrabutylammonium kaolinite were investigated by K.G. Bhattacharyya et al.

structure, high mechanical strength and remarkable electrical conductivity.

The removal rate of Cr(VI)

The bisorption by various biosorbents such as coconut shell, wheat bran

carbons using plant biomass is generating a diversity of activated carbon with

2.3.3 Batch adsorption experiment

where, qe (mg/g) is the equilibrium adsorption capacity, C0 and Ce are the

Maximum adsorption of Cr(VI) was observed at the acidic pH. This is

2HCrO4 Cr2O7 2 + H2O

coexist of which HCrO4

2.4.5 Effect of agitation speed

2.4.7 Langmuir isotherm

The desorption from the surface is proportional to the amount of surface

Where kL and kd are rate coefficients for adsorption and desorption, ra is

Putting Eq. (12) in Eq. (15)

Dividing Eq. (16) by kd

The saturated monolayer sorption capacity, qm, can be obtained. When

Inverting Eq. (19), we get

where, Ce is the equilibrium concentration (mg/dm3); qe is the amount of metal

where, Kf is the measure of adsorption capacity and n is the adsorption

where, qe is the amount adsorbed (mg/g), Ce is the equilibrium concentration of

solutions [105]. The value of the correlation coefficient, R , obtained in this

Several kinetic models are in use to explain the mechanism of the

2.4.10 Intraparticle diffusion study

The equilibrium constants Kc was evaluated at each temperature using the

2.5 COMPARISON OF ADSORPTION CAPACITY OF WASAC WITH

Amount adsorbed, q mg/g

Amount adsorbed, qt mg/g

Amount adsorbed, q mg/g

pseudo second order

Amount adsorbed, q mg/g

Acid modified waste activated carbon

Short chain polyaniline (PANI)

Turkish Afsin-Elbistan fly ash

Seyitomer fly ash

Bagasse fly ash

Coal fly ash

Beech (Fagus orientalis L.) sawdust

Pre-boiled sunflower stem

Formaldehyde treated sunflower stem

Bael fruit (Aegle marmelos correa)

Sulfuric acid treated Groundnut husk

Silver nitrate impregnate

Oak saw dust

Coconut tree saw dust

Coconut shell carbon

Waste biogas slurry

Indian Rosewood sawdust

Ficus religiosa leaves

Sal (Shorea robusta)

Wood apple shell

Amount adsorbed of Cr(VI), mg/g

Amount adsorbed of Cr(VI), mg/g

Amount adsorbed of Cr(VI), mg/g

Initial conc. of Cr(VI), mg/dm

Amount adsorbed of Cr(VI), mg/g

Amount adsorbed of Cr (VI), mg/g

F. Gholami, A. H.Mahvi, Gh. A.Omrani, S.Nazmara, A. Ghasri,